Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
  • C08K5/3432—Six-membered rings
  • C08K5/3435—Piperidines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
  • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
  • C08L27/06—Homopolymers or copolymers of vinyl chloride
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
  • C08L25/02—Homopolymers or copolymers of hydrocarbons
  • C08L25/16—Homopolymers or copolymers of alkyl-substituted styrenes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
  • C08L27/22—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers modified by chemical after-treatment
  • C08L27/24—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers modified by chemical after-treatment halogenated
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/24—Homopolymers or copolymers of amides or imides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L35/06—Copolymers with vinyl aromatic monomers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds

Definitions

• the present invention relates to a thermoplastic resin composition of improved weather resistance.
• Vinyl chloride resin articles have problems of impact resistance and heat resistance and many attempts have been made to improve these properties.
• One approach to improving impact resistance is to blend chlorinated polyethylene, ethylene-vinyl acetate copolymer to which vinyl chloride is grafted or impact strength modifiers such as acrylic rubber with the resin articles, taking into consideration the desired weather resistance.
• Another approach for improving impact resistance as well as heat resistance is to blend with vinyl chloride resin the above impact strength modifier and a heat resistance modifier such as ⁇ -methylstyreneacrylonitrile copolymer.
• light stabilizers made from hindered amine which trap radicals produced by heat or light energy do not perform sufficiently as light stabilizers for vinyl chloride resins.
• An object of the present invention is to provide a vinyl chloride resin composition having improved impact resistance or both the impact resistance and heat resistance and enhanced weather resistance without damaging the excellent processing stability and mechanical strengths.
• hindered amine light stabilizers which do not exhibit sufficient effect as light stabilizers for vinyl chloride resins markedly improve weather resistance of a polymer mixture which comprises a vinyl chloride polymer or a mixture of a vinyl chloride polymer and a polymer containing no chlorine and having a glass transition temperature of 100 - 200°C and an impact strength modifier containing no double bond which consists of an ethylene/methyl methacrylate copolymer on which vinyl chloride is grafted and an acrylic rubber.
• JP-A-55050047 quoted in Patent Abstracts of Japan page 99 column 15 reveals a composition containing a vinyl chloride polymer and a second polymer containing no chlorine, an impact strength modifier and a benzotriazole or a benzophenone light stabilizer.
• thermoplastic resin composition superior in weather resistance which comprises (1) 100 parts by weight of a mixture comprising 100 - 40, preferably 40 to 95, parts by weight of a vinyl chloride polymer and 0 - 60, preferably 5 to 60, parts by weight of a second polymer containing no chlorine and which has a glass transition temperature of 100 - 200°C, (2) 4 - 25 parts by weight of an impact strength modifier and (3) 0.1 - 1.0 part by weight of a hindered amine light stabilizer, characterised in that the impact strength modifier contains no double bonds and consists of an ethylene/methyl methacrylate copolymer on which vinyl chloride is grafted and an acrylic rubber and in that the hindered amine light stabilizer is bis-(2,2,6,6,-tetramethyl-4-piperidinyl) sebacate, or is of the formula: and has an average molecular weight of 2500 or more.
• the component (1) comprises vinyl chloride polymers. They include vinyl chloride homopolymer and copolymers comprising at least 90% by weight of a vinyl chloride monomer and up to 10% by weight of a monoolefin copolymerizable with the vinyl chloride monomer, for example, vinyl acetate or vinylidene chloride.
• the polymers may be produced by suspension polymerization, bulk polymerization, emulsion polymerization, etc.
• the chlorinated vinyl chloride polymers used in the present invention may be produced by known process, for example, by suspending in water a vinyl chloride polymer with or without a chlorinated hydrocarbon solvent, and then applying chlorine-addition thereto.
• This chlorinated vinyl chloride polymer is added preferably in an amount of 5 - 50%, more preferably 10 - 40% by weight of vinyl chloride polymer. If the amount is less than 5% by weight, improvement of heat resistance is not sufficient and if more than 50% by weight, processing stability is insufficient.
• the second polymers containing no chlorine and having a glass transition temperature of 100 - 200 ° C which may be used as one of the components in the vinyl chloride mixture (1) are those which enhance heat resistance of vinyl chloride resins. They are, for example, poly ⁇ -methylstyrene, copolymers mainly formed of ⁇ -methylstyrene such as ⁇ -methylstyrene/acrylonitrile copolymer, imide polymers such as poly N-phenylmaleimide or polyglutarmaleimide, and styrene/maleic anhydride copolymer.
• ⁇ -methylstyrene/acrylonitrile copolymer Preferred are ⁇ -methylstyrene/acrylonitrile copolymer, polyglutarmaleimide and styrene/maleic anhydride copolymer, taking into consideration their compatibility with vinyl chloride polymer and enhancement of heat resistance.
• the glass transition temperature is the point at which the gradient of the volume-temperature curve according to dilatometer measurements abruptly changes and if this is lower than 100°C, enhancement of heat resistance is insufficient and if this is higher than 200°C, processing temperature is naturally high and processing stability of the vinyl chloride resin composition is inferior.
• the amount of the latter polymer i.e., that containing no chlorine, should preferably be 0 - 60 parts by weight for every 100 parts by weight of (1).
• the latter polymer should be 5 - 60 parts, preferably 20 - 60 parts. If more than 60 parts by weight is used, impact resistance decreases.
• the impact strength modifier should be added in an amount of 4 - 25 parts, preferably 5 - 20 parts by weight every 100 parts by weight of component (1). If it is less than 4 parts by weight, improvement of impact resistance is lower and if more than 25 parts by weight, mechanical strength is lower.
• the hindered amine stabilizer is added in an amount of 0.1 - 1.0 parts, more preferably 0.2 - 0.8 parts, by weight on the basis of 100 parts by weight of component (1) above. If the amount is less than 0.1 part by weight, improvement of weather resistance is insufficient and even if it is more than 1.0 parts by weight, the effect is not increased so much.
• composition of the present invention there may be optionally added known stabilizers, lubricants, ultraviolet ray absorbers, antioxidants, pigments, etc. which are commonly used for processing of vinyl chloride resins and furthermore, if necessary, fillers may also be used.
• Components (1) - (3) above may be mixed by roll mills, ribbon blenders, Henschel mixers, Banbury mixers, etc. and may be processed into desired molded articles by known molding machines such as extruders, injection molding machines or calendering machines.
• the resulting molded articles are of high mechanical strength and excellent impact resistance and heat resistance and besides have improved weather resistance. Therefore, they are useful as rigid articles such as pipes and building materials.
• Evaluation of weather resistance Charpy impact strength measured in accordance with JIS K7111 on a sample subjected to exposure for 300 hours under the conditions of black panel temperature of 63°C and spraying of 18 min/120 minutes using a sunshine weatherometer type accelerated weathering apparatus specified in JIS A1415.
• Charpy impact strength after exposure for 300 hr x 100 Charpy impact strength before exposure
• a resin composition comprising a polymer mixture of polyvinyl chloride having an average polymerization degree of 1100 (100 parts; "Sumilit”® SxllF of Sumitomo Chemical Co., Ltd.), graft polymer A (6 parts) prepared by the following process and acrylic rubber (6 parts; Kane Ace FM of Kanegafuchi Chemical Industry Co., Ltd.), were added a lead stabilizer (3 parts), a metallic soap lubricant (1 part), a processability modifier (1.5 parts), a pigment (0.8 part) and a hindered amine stabilizer (0.3 part; Chimassorb 944LD of Ciba-Geigy Corp.).
• the blend was kneaded and extruded to shape pipes by a different direction twin-screw extruder Mitsubishi Kraus KMD-60K at 25 rpm under the following temperature conditions: cylinders: C 1 165°C, C 2 160°C, C 3 170°C and C 4 175°C, adapter: Ad 170°C, dies: D 1 160°C, D 2 153°C, D 3 167°C and D 4 180°C.
• Mechanical strength, heat resistance, weather resistance and impact resistance of the resulting pipes were measured.
• dynamic heat stability of the above composition was also measured by the above mentioned method. The properties are shown in Table 1B.
• Dionized water 100 parts
• ethylene/methyl methacrylate copolymer 50 parts; "Acryft” ® WM-305 of Sumitomo Chemical Co., Ltd.
• hydroxypropylmethyl cellulose 0.2 part; "Metholose”® 65SH-50 of Shinetsu Chemical Co., Ltd.
• ⁇ , ⁇ '-azobisisobutyronitrile 0.08 part
• diallyl phthalate 0.5 part
• graft polymer A which contained 59% of ethylene/methyl methacrylate copolymer and had 43% of gel content insoluble in tetrahydrofuran.
• Example 1 was repeated except that Kane Ace FM (6 parts) was used in place of the graft copolymer A (6 parts).
• the properties are shown in Table 1B. This is a comparison example.
• Example 1 was repeated except that 20 parts of "Sumilit” R SxllF (100 parts) was replaced by chlorinated vinyl chloride polymer (heat resistance Kanevinyl of Kanegafuchi Chemical Industry Co., Ltd.). The properties are shown in Table 1B.
• Example 1 was repeated except that hindered amine stabilizer Sanol LS-770 (Sankyo Co., Ltd.) was used in place of the Chimassorb 944LD.
• the properties are shown in Table 1B.
• Example 1 was repeated except that amounts of Sumilit Sx11F, the graft copolymer A, Kane Ace FM, and Chimassorb 944LD were changed as shown in Table 1. The properties are shown in Table 1B.
• Example 1 was repeated, except that a benzotriazole ultraviolet ray absorber (Sumisorb 300 of Sumitomo Chemical Co., Ltd.) was used in place of the Chimassorb 944LD.
• a benzotriazole ultraviolet ray absorber (Sumisorb 300 of Sumitomo Chemical Co., Ltd.) was used in place of the Chimassorb 944LD.
• the properties are shown in Table 1B.
• Example 1 was repeated except that amount of the pigment (0.8 part) was changed to 3.0 parts and TiO 2 (2.0 parts) was used in place of Chimassorb 944LD.
• the properties are shown in Table 1B.
• Example 1 was repeated except that amounts of the Sumilit SxllF, graft polymer A, Kane Ace FM and Chimassorb 944LD were changed. The properties are shown in Table 1B.
• Example 1 was repeated except that 80 parts of the Sumilit Sx11F (100 parts) was replaced by chlorinated vinyl chloride polymer. The properties are shown in Table 1B.
• Samples of Comparative Example 1 are lower in weather resistance and those of Comparative Example 2 are higher in lubrication and impact resistance is lower because a large amount of pigment is added for colour matching.
• Samples of Comparative Example 3 are lower in tensile strength and Vicat softening point and those of Comparative Example 4 are lower in Charpy impact strength.
• Samples of Comparative Example 5 are lower in weather resistance and those of Comparative Example 6 are lower in dynamic heat resistance and in processing stability.
• the properties are shown in Table 2A1 and 2A2.
• Example 9 was repeated except that the graft polymer A (5 parts) was changed to Kane Ace FM, namely, Kane Ace (15 parts) was used.
• the properties are shown in Table 2A1 and 2A2. This is a comparison example.
• Example 9 was repeated except that 15 parts of the Sumilit Sx11F (55 parts) was replaced by heat resistant Kanevinyl. The properties are shown in Table 2A1 and 2A2.
• Example 9 was repeated except that amounts of the polymer and Chimassorb 944LD to be added were changed. The properties are shown in Table 2A1 and 2A2.
• Example 15 is a comparison example.
• the resin compositions of Examples 9 - 16 all show good dynamic heat stability and molded articles obtained from these resin compositions not only have high Charpy impact strength retention after being subjected to the weathering test for 300 hours, but also are superior in mechanical strength, impact resistance and heat resistance.
• Example 9 was repeated except that Sumisorb 300 was used in place of the Chimassorb 944LD.
• the properties are shown in Table 2B1 and 2B2.
• Example 9 was repeated except that the amount of the pigment (0.8 part) was increased to 3.0 parts and TiO 2 (2.0 parts) was used in place of the Chimassorb 944LD.
• the properties are shown in Table 2B1 and 2B2.
• Example 9 was repeated except that amounts of the polymer and light stabilizer Chimassorb 944LD to be added were changed. The properties are shown in Table 2B1 and 2B2.
• Example 9 was repeated except that 40 parts of the Sumilit SxllF (55 parts) was replaced by heat resistant Kanevinyl. The properties are shown in Table 2B1 and 2B2.
• Samples of Comparative Example 7 are of lower weather resistance and those of Comparative Example 8 are higher in lubrication and impact resistance is lower because a large amount of pigment is added for colour matching.
• Samples of Comparative Example 9 are lower in tensile strength, Vicat softening point and Charpy impact strength and those of Comparative Examples 10 and 11 are lower in Charpy impact strength and that of Comparative Example 12 is lower in tensile strength and Vicat softening point.
• Samples of Comparative Example 13 are lower in weather resistance and those of Comparative Example 14 are lower in dynamic heat resistance and in processing stability.
• thermoplastic resin composition of the present invention is superior processing stability and molded articles made therefrom show markedly excellent weather resistance and superior mechanical properties represented by tensile strength, flame retardance and chemical resistance and besides are improved in impact resistance or heat resistance and impact resistance.
• the compositions may be used as pipes or building materials which are subjected to severe conditions, in view of the features above. More specific uses are electric wires and underground pipes.
• Formulae I available from Nihon Chiba-Geigy Co. as CHIMASSORB 944LD (Registered Trade Mark). It has an average molecular weight of 2500 or more, the formula is: Formula II is available from Sankyo Co. as SANOL L770 (Registered Trade Mark). It is bis-(2,2,6,6-tetramethyl-4-piperidinyl) sebacate namely:

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• 1989
  • 1989-09-27 EP EP89309848A patent/EP0366271B2/en not_active Expired - Lifetime
  • 1989-09-27 DE DE68913267T patent/DE68913267T3/de not_active Expired - Fee Related
  • 1989-09-28 KR KR1019890013958A patent/KR950010117B1/ko not_active IP Right Cessation
• 1994
  • 1994-01-21 US US08/183,792 patent/US5378745A/en not_active Expired - Fee Related

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